Phosphite sulfonate reaction products as multifunctional additives

ABSTRACT

Phosphites of hydrocarbyl diols or alkoxylated amines are reacted with aryl sulfonic acids preformed or formed in situ in lubricants to provide multifunctional antioxidant, corrosion inhibiting, and friction reducing properties therefor.

BACKGROUND OF THE INVENTION

This application is directed to the use of additive concentrations ofneutralized metallic hydrocarbyl sulfonate/dialkyl cyclic (ornon-cyclic) phosphite reaction products in premium quality industrial,automotive and marine lubricants which provide a "time-release" dosageof multifunctional friction reducing antiwear properties and thus extendservice life.

Lubricants, such as lubricating oils and greases, are subject tooxidative deterioration at elevated temperatures or upon prolongedexposure to the elements. Such deterioration is evidenced, in manyinstances, by an increase in acidity and in viscosity, and when thedeterioration is severe enough, it can cause metal parts to corrode.Additionally, severe oxidation leads to a loss of lubricationproperties, and in especially severe cases this may cause completebreakdown of the device being lubricated. Many additives have beentried. However, many of them are only marginally effective except athigh concentrations. Improved antioxidants are clearly needed.

Antioxidants or oxidation inhibitors are used to minimize the effects ofoil deterioration that occur when hot oil is contacted with air. Thedegree and rate or oxidation will depend on temperature, air and oilflow rates and, of particular importance, on the presence of metals thatmay catalytically promote oxidation. Antioxidants generally function byprevention of chain peroxide reaction and/or metal catalystdeactivation. They prevent the formation of acid sludges, darkening ofthe oil and increases in viscosity due to the formation of polymericmaterials.

Water (moisture) is another critical problem. In spite of evenextraordinary precautionary efforts water is found as a film or inminute droplets in vessels containing various hydrocarbon distillates.This brings about ideal conditions for corrosion and damage of metalsurfaces of the vessels and the materials contained therein. Also in thelubrication of internal combustion engines, for example, quantities ofwater are often present as a separate phase within the lubricatingsystem. Another serious problem in respect to metallic surfaces incontact with adjacent metallic surfaces is the surface wear caused bythe contact of such surfaces. One material capable of simultaneouslyeffectively coping with such problems as these is highly desirable.

Lubricants in service applications often generate acid species oracid-forming species, especially when exposed to high operatingtemperatures, extended service life and/or contact with atmosphericoxygen during aeration caused by churning or moving elements of thelubricated machine. Acid-forming species can also be formed viahydrolysis or other similar mechanisms.

Metallic aryl sulfonates such as calcium dinonylnaphthalene sulfonateshave been widely used in petroleum and synthetic lubricants as rust andcorrosion inhibiting additives. Additionally, these and related metallicaryl sulfonates have, on occasion, provided good detergency anddemulsibility properties in a variety of lubricant formulations.

It has now been found that if metallic aryl sulfonates are used asadditives in systems as described above, neutralization or acidificationto form sulfonic acids can occur. If both metallic aryl sulfonates anddi- or trialkyl diol or alkoxylated amine phosphites are used togetherin a lubricant, or alternatively pre-reacted, these sulfonic acids andphosphites can react to form sulfonate esters and lower phosphiteshaving one less alkyl substitutent group. This mechanism can thusprovide a "time-release" dosage of friction reducing, corrosioninhibiting or antiwear additives during the latter stages of lubricantservice life when performance improvement is most needed. This phenomenacan also be effectively used to neutralize potentially harmful acidsubstances as soon as they are generated. These remarkable benefits canbe provided for a variety of synthetic and mineral oil based lubricants.

It is an object of this invention to provide both (a) a unique lubricantadditive composition made by the reaction of at least partiallyneutralized or acidified sulfonates with alkanediol or alkoxylated aminephosphites, and (b) a method of providing for "time release" frictionreducing, corrosion inhibiting, and/or antiwear properties viaappropriate blending of sulfonate and phosphite components, allowing forthe acidification or neutralization of the sulfonate in situ, in serviceand then the co-reaction of the acidified sulfonate and diol oralkoxylated amine phosphite while in use.

To the best of our knowledge the compositions in accordance with theinvention have not been previously used as multifunctional additives inlubricating oils or greases or other solids lubricants. The use ofreaction products of acidified sulfonates and cyclic phosphites oralkoxylated amine phosphites as multifunctional additives has not beenreported in the literature and are believed to be novel. The compositionof matter, the lubricant compositions containing such additives, and theuse of such reaction products and lubricants to improve the performanceproperties are also unique.

The use of sulfonates and diol-derived or alkoxylated amine phosphitesas "time-release" multifunctional additives for lubricants whichfunction via at least partial neutralization or acidification followedby phosphite esterification is also believed to be both unique andnovel.

SUMMARY OF THE INVENTION

In accordance with the invention there is provided by the use ofadditive concentrations of at least partially neutralized or acidifiedmetallic hydrocarbyl sulfonate/hydrocarbyl (dialkyl) cyclic phosphitereaction products in premium quality industrial, automotive and marinelubricants, superior lubricating fluids which provide a "time-release"dosage of multifunctional friction reducing antiwear properties and thusextend service life. Hydrocarbyl as used herein includes but is notlimited to alkyl, alkenyl, aryl, alkenyl, alkaryl, aralkyl, andcycloalky, and/or mixtures thereof. The unique compositions described inthis patent application are readily prepared in a one-pot process inexisting equipment using known technology. With these "time-release"EP/antiwear, friction reducing additives providing in-situ reaction byappropriate blending of sulfonate/phosphite (cyclic or non-cyclic)additive components extended service life premium lubricants areprovided.

DESCRIPTION OF SPECIFIC EMBODIMENTS

Metallic hydrocarbyl aryl sulfonates can be neutralized or acidified inservice, in situ, or via addition of small quantities of organic orinorganic acids, as shown below:

    (ArSO.sub.3).sub.n M+nH.sup.+ →nArSO.sub.3 H+M.sup.n+

where n is an integer equal to the valence number of M, Ar is a C₁₂ toabout C₃₂ dialkylnaphthalene, or dihydrocarbylarene, or any alkylaromatic, and M is alkali metal, or alkaline-earth metal and/or anitrogenous group such as amine or ammonium. The above acid can thenreact in service or in situ with any phosphite, preferably cyclic oramine-containing phosphite to form multifunctional additives withenhanced antiwear, friction reducing and/or corrosion inhibitingproperties. The non-traditional phosphites include cyclic phosphites oflong-chain or short-chain diols, and phosphites of alkoxylatedhydrocarbyl amines including phosphites ofbis(2-hydroxyethyl)oleylamine, polyethoxylated tallowamine,2-hydroxypropylcocoamine, and the like. The phosphites are made byreaction of a dihydrocarbyl phosphite with the appropriate hydroxylgroup containing moiety such as diol or alkoxylated amine.

The alkoxylated amine and amine-phosphites are as generally described inU.S. Pat. No. 4,557,845 which is incorporated herein in its entirety byreference thereto. The amines useful herein can also be alkoxylatedhydrocarbyl diamines, or alkoxylated etheramines. Usually theamine-phosphites are prepared by reacting an alkoxylated hydrocarbylamines of the following generalized formula: ##STR1## wherein R² is a C₆to about C₃₀ hydrocarbyl group or sulfur, nitrogen and/oroxygen-containing hydrocarbyl group, R³ is hydrogen or a C₁ to C₆hydrocarbyl group, and x and y are intergers of from 0 to 50, at leastone of which is not 0, with a phosphite of the following generalizedformula: ##STR2## wherein R⁴ is a C₁ to C₆ hydrocarbyl group and R⁵ ishydrogen or a C₁ to C₆ hydrocarbyl group preferably hydrocarbyl is alkylor mixtures thereof.

Preferred alkoxylated amines include but are not limited to the groupconsisting of 2-hydroxyethylhexylamine, 2-hydroxyethyloctylamine,2-hydroxyethyldodecyclamine, 2-hydroxyethyltetradecylamine,2-hydroxyethyleicosylamine, 2-hydroxyethyltriacontylamine,2-hydroxyethyloleylamine, 2-hydroxyethyltallowamine,2-hydroxyethylsoyamine, bis(2-hydroxyethyl)hexylamine,bis(2-hydroxyethyl)octylamine, bis(2-hydroxyethyl)dodecylamine,bis(2-hydroxyethyl) tetradecylamine, bis(2-hydroxyethyl)pentadecylamine,bis(2-hydroxyethyl)eicosylamine, bis(2-hydroxyethyl)-triacontylamine,bis(2-hydroxyethyl)oleylamine, bis(2-hydroxyethyl)tallowamine,bis(2-hydroxyethyl) soyamine, 2-hydroxypropylhexylamine,2-hydroxypropyloctylamine, 2-hydroxypropdodecylamine,2-hydroxypropyltetradecylamine, 2-hydroxypropylpentadecylamine,2-hydroxypropyleicosylamine, 2-hydroxypropyltriacontylamine,2-hydroxypropyloleylamine, 2-hydroxypropyltallowamine,2-hydroxypropylsoyamine, bis(2-hydroxypropyl)hexylamine,bis(2-hydroxypropyl)octylamine, bis(2-hydroxypropyl)dodecylamine,bis(2-hydroxypropyl)tetradecylamine,bis(2-hydroxypropyl)pentadecylamine, bis(2-hydroxypropyl)eicosylamine,bis(2-hydroxypropyl)triacontylamine, bis(2-hydroxypropyl)oleylamine,bis(2-hydroxypropyl)soyamine or mixtures thereof.

The hydrocarbyl or dihydrocarbyl diol derived phosphites are asgenerally described in U.S. Pat. No. 4,704,218 which is incorporatedherein in its entirety by reference thereto and have the generalizedformula:

    R.sup.1 (OH).sub.2

wherein R¹ is a hydrocarbyl group having from 10 to about 30 carbonatoms, R¹ can also optionally contain N, S, and/or O.

Included are phosphites derived from diol esters such as glycerolmonooleate, glycerol monohexanoate or any glycerol monoester;trimethylolpropane monooleate, trimethylolpropane monostearate,trimethylolpropane monohexanate or similar monoesters; pentaerythritoldidecanoate, pentaerythritol diisostearate or similar diesters. Althoughcyclic phosphites are preferred non-cyclic or oligomeric phosphites canalso be used. The phosphites are as described in either U.S. Pat. Nos.4,557,845 or 4,704,218 and have the generalized formula: ##STR3##wherein said R is a C₁ to a C₆ hydrocarbyl group preferably alkyl ormixtures thereof and hence preferably selected from methyl, ethyl,propyl, butyl, pentyl, hexyl or mixtures thereof.

Preferred diols include but are not limited to the group consisting of1,2-decanediol, 1,2-dodecanediol, 1,2-tetradecanediol,1,2-pentadecanediol, 1,2-hexadecanediol, 1,2-heptadecanediol,1,2-octadecanediol and mixtures thereof and as noted hereinabove diolesters.

The reactants are preferably used in equimolar quantities although lessthan molar or more than molar quantities may be used. The inventiontherefore contemplates products made by using molar ratios of sulfonateto amine-phosphite or diol-phosphite of 10:1 to about 1:10.

The temperature of reaction will depend upon the solvent used, since thereaction will generally be run at the temperature of reflux. Thetemperature is not believed to be critical and the reaction can be runover a wide range, from about 50° to about 225° C., preferably fromabout 80° to about 150° C.

Although a solvent is not required, examples of useful solvents includebut are not limited to toluene, benzene, xylene, cyclohexane, ethanoland the like. Where a solvent is used, it should be one in which theproducts are soluble and which can be relatively easily removed,although in some cases a lubricating oil can be used as a solvent and/ordiluent.

Times of reaction are not critical, but they will vary depending uponthe size and complexity of the reactants. Under normal conditions, thereaction with the contemplated reactants can be completed in from aboutone hour to about ten hours or more preferably from about two hours toabout six hours.

Other additives, such as detergents, dispersants, antioxidants, antiwearagents, extreme pressure additives, pour depressants, antirust additivesand the like may be present in the compositions of the presentinvention. These can include phenates, sulfonates, polymericsuccinimides, zinc dialkyl or aryl dithiophosphates, polymers, calciumand magnesium salts, polymeric viscosity index improving additives suchas olefin copolymers, sulfurized olefins and the like.

The compounds of the invention are used with lubricating oils or greasesto the extent of from about 0.01% to about 10% by weight of the totalcomposition, preferably from about 0.2% to about 2%.

The lubricants contemplated for use with the novel additive productsherein disclosed include mineral and synthetic hydrocarbon oils oflubricating viscosity, mixtures of mineral oils and synthetic oils andgreases from any of these, including the mixtures. The synthetichydrocarbon oils include long-chain alkanes such as cetanes and olefinpolymers such as oligomers of hexene, octene, decene and dodecene, etc.Vicinal diol-derived phosphites are especially effective in syntheticoils formulated using mixtures of synthetic hydrocarbon olefin oligomersand lesser amounts of hydrocarbyl carboxylate ester fluids. The othersynthetic oils, which can be used alone with the compounds of thisinvention, or which can be mixed with a mineral or synthetic hydrocarbonoil, include (1) fully esterified ester oils, with no free hydroxyls,such as pentaerythritol esters of monocarboxylic acids having 2 to 20carbon atoms, trimethylolpropane esters of monocarboxylic acids having 2to 20 carbon atoms, (2) polyacetals and (3) siloxane fluids. Especiallyuseful among the synthetic esters are those made from polycarboxylicacids and monohydric alcohols. More preferred are the ester fluids madeby fully esterifying pentaerythritol, or mixtures thereof with di-andtripentaerhthritol, with an aliphatic monocarboxylic acid containingfrom 1 to 20 carbon atoms, or mixtures of such acids.

A wide variety of thickening agents can be used in the greases of thisinvention. Included among the thickening agents are alkali and alkalineearth metal soaps of fatty acids and fatty minerals having from about 12to about 30 carbon atoms per molecule. The metals are typified bysodium, lithium, calcium and barium. Fatty materials are illustrated bystearic acid, hydroxystearic acid, stearin, cottonseed oil acids, oleicacid, palmitic acid, myristic acid and hydrogenated fish oils.

Other thickening agents include salt and salt-soap complexes such ascalcium stearate-acetate (U.S. Pat. No. 2,197,263), barium stearateacetate (U.S. Pat. No. 2,564,561), calcium stearate-caprylate-acetatecomplexes (U.S. Pat. No. 2,999,065), calcium caprylate-acetate (U.S.Pat. No. 2,999,066), and calcium salt and soaps of low-, intermediate-and high-molecular weight acids and of nut oil acids.

Another group of thickening agents comprises substituted ureas,phthalocyanines, indanthrene, pigments such as perylimides,pyromellitdiimides, and ammeline.

The preferred thickening/gelling agents employed in the greasecompositions are essentially hydrophobic clays. Such thickening agentscan be prepared from clays which are initially hydrophilic in character,but which have been converted into a hydrophobic condition by theintroduction of long chain hydrocarbon radicals into the surface of theclay particles; prior to their use as a component of a greasecomposition, as, for example, by being subjected to a preliminarytreatment with an organic cationic surface active agent, such as anonium compound. Typical onium compunds are tetraalkylammonium chlorides,such as dimethyl dioctadecyl ammonium chloride, dimethyl dibenzylammonium chloride and mixtures thereof. This method of conversion, beingwell known to those skilled in the art, is believed to require nofurther disucssion, and does not form a part of the present invention.

More specifically, the clays which are useful as starting materials informing the thickening agents to be employed in the grease compositions,can comprise the naturally occurring chemically unmodified clays. Theseclays are crystalline complex silicates, the exact composition of whichis not subject to precise description, since they vary widely from onenatural source to another. These clays can be described as complexinorganic silicates such as aluminum silicates, magnesium silicates,barium silicates, and the like, containing, in addition to the silicatelattice, varying amounts of cation-exchangeable groups such as sodium.Hydrophilic clays which are particularly useful for conversion todesired thickening agents include montmorillonite clays, such asbentonite, attapulgite, hectorite, illite, saponite, sepiolie, biotite,vermiculite, zeolite clays, and the like.

The following examples typify but are not meant in any way to limit theinvention.

CYCLIC PHOSPHITE-ARYL SULFONIC ACID REACTION PRODUCT Example 1

A one liter, four-neck flask was equipped with thermometer, N₂ sparger,condenser, and agitator. Approximately 112 g mol of calciumdinonylnaphthalene sulfonate (commercially obtained from KingIndustries, Inc. as Nasul 729) in 100 ml of toluene was charged to thereactor and acidified with 4.9 ml of 30% sulfuric acid and reacted forone hour at 60° C. A mixed hexadecane- and octadecane-1,2-diol phosphite(38 g, 0.12 mol) was then added in one portion. This phosphite wasprepared as generally described in U.S. Pat. No. 4,532,057 which isincorporated as a reference in its entirety. The mixture was heated toreflux for four hours, filtered and washed with toluene. The combinedfiltrate and washings were washed with water (2×50 ml), dried over MgSO₄and evaporated under a reduced pressure at 110° C. yield 158 g ofviscous brown fluid.

ALKOXYLATED AMINE-PHOSPHITE-ACIDIFIED Sulfonate Reaction Product Example2

To a stirred solution of bis(2-hydroxyethyl)oleylamine (35.2 g, 0.10mol) in 100 ml of toluene was added tributyl phosphite (25 g, 0.10 mol)dropwise under N₂ atmosphere. The mixture was heated to 70° C. for twohours before 96 g of Nasul 729 was added. The mixture was stirred at 90°C. for one hour, then 4 ml of 30% sulfuric acid was charged to thereaction mixture, and was further heated to reflux for four hours. Thefinal mixture was filtered, the filtrate was washed with water, dried,and evaporated under a reduced pressure at 120° C. to yeild 133 g ofbrown fluid.

Evaluation of Products

The product of the examples were evaluated using the Catalytic OxidationTest as shown in Tables 1 and 2 below. The results demonstrate theremarkable antioxidant features of the examples with respect to controlof the increase in viscosity and acidity. The Catalytic Oxidation Testmay be summarized as follows: Basically the lubricant is subjected to astream of air which is bubbled through the oil formulation at the rateof 5 liters per hour at 325° F. for 72 hours (Table 1) and 40 hours(Table 2) respectively. Present in the composition are samples of metalscommonly used in engine construcion, namely iron, copper, aluminum andlead, see U.S. Pat. No. 3,682,980 incorporated herein by reference forfurther details.

                  TABLE 1                                                         ______________________________________                                        Catalytic Oxidation Test                                                      325° F., 72 Hours                                                                      Change in  Percent Change in                                                  Acid Number                                                                              Kinematic Viscosity                                Item            Δ TAN                                                                              Δ KV %                                       ______________________________________                                        Base oil (100% solvent                                                                        8.16       110.0                                              paraffinic neutral mineral                                                    oil)                                                                          1% of Example 1 5.25       22.2                                               1% of Example 2 5.91       31.5                                               ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Catalytic Oxidation Test                                                      325° F., 40 Hours                                                                    Change in  Percent Change in                                                  Acid Number                                                                              Kinematic Viscosity                                  Item          Δ TAN                                                                              Δ KV %                                         ______________________________________                                        Base oil (100% solvent                                                                      6.63       66.3                                                 paraffinic neutral                                                            mineral oil)                                                                  1% of Example 1                                                                             0.47       4.6                                                  1% of Example 2                                                                             0.74       6.6                                                  ______________________________________                                    

The examples were also evaluated in accordance with standard corrosiontest, ASTM-D 130-80 for copper strip corrosion at 250° F. for threehours. Both samples gave a rating of 1A which means substantially nocorrosion for the test.

The antiwear properties of the examples were also evaluated using theFour Ball Wear Test data as shown in Table 3. The results clearlyexhibit the good antiwear properties inherent in these unuiqecompositions.

In the Four Ball Wear Test three stationary balls are placed in alubricant cup and a lubricant containing the compound to be tested isadded thereto, and a fourth ball is placed in a chuck mounted on adevice which can be used to spin the ball at known speeds and loads. Theexamples were tested using half inch stainless steel balls of 5 to 100steel for 30 minutes under a 60 Kg load at 2000 rpms and 200° F. Ifadditional information is desired consult test method ASTM D2266 and/orU.S. Pat. No. 4,761,482.

                  TABLE 3                                                         ______________________________________                                        Four-Ball Wear Test                                                                                Wear Scar Diameter in                                                         mm, 30 minute test,                                                           60 Kg load, 2000 RPM                                     Item                 at 200° F.                                        ______________________________________                                        Base oil (80% solvent paraffinic                                                                   3.78                                                     bright, 20% solvent paraffinic                                                neutral minera1 oils)                                                         1% of Example 1      1.82                                                     1% of Example 2      1.62                                                     ______________________________________                                    

The data clearly illustrate (a) the method of providing "time release"antiwear property by blending appropriate sulfonate and cyclic phosphitecomponents, and (b) use of the unique additive composition made byesterification of partially neutralized sulfonate with cyclic phosphitesfor use in lubricants and greases.

Although the present invention has been described with preferredembodiments, it is to be understood that modifications and variationsmay be resorted to, without departing from the spirit and scope of thisinvention, as those skilled in the art will readily understand. Suchmodifications and variations are considered to be within the purview andscope of the appended claims.

What is claimed is:
 1. A product of reaction obtained by reacting apartially acidified hydrocarbyl sulfonate having from about 12 to about32 carbon atoms with a phosphite derived from a diol or an amine, andhaving from about 10 to about 30 carbon atoms, the reaction beingcarried out at from about 50° C. to about 225° C. using a mole ratio ofsulfonate to phosphite of from about 10:1 to about 1:10.
 2. The productof claim 1 wherein the hydrocarbyl sulfonate is of the general formula:

    (ArSO.sub.3).sub.n M

where n is an integer equal to the valence number of M,M is (1) alkalimetal or alkaline earth metal, (2) a nitrogenous group or a mixture of(1) and (2) and Ar is a C₁₂ to about a C₃₂ dialkylnaphthalene,dihydrocarbylarene or alkylaromatic group.
 3. The product of claim 2wherein M is an alkaline earth metal.
 4. The product of claim 3 whereinM is selected from calcium or barium, or magnesium.
 5. The product ofclaim 4 wherein M is calcium.
 6. The product of claim 5 wherein thehydrocarbyl sulfonate is calcium dinonylnaphthalene sulfonate.
 7. Theproduct of claim 1 wherein the amine derived phosphite is prepared fromamines selected from the group consisting of alkoxylated amines,alkoxylated hydrocarbyl amines, alkoxylated hydrocarbyl diamines,alkoxylated ether amines and mixtures thereof.
 8. The product of claim 1wherein the amine phosphite is made by reacting an alkoxylated amine ofthe formula: ##STR4## wherein R² is a C₆ to about C₃₀ hydrocarbyl groupor a C₆ to about C₃₀ sulfur, nitrogen or oxygen-containing hydrocarbylgroup or a mixture thereof, R³ is hydrogen or a C₁ to C₆ hydrocarbylgroup, and x and y are integers of from 0 to 50, at least one of whichis not 0, with a phosphite of the formula: ##STR5## wherein R⁴ is a C₁to C₆ hydrocarbyl group and R⁵ is hydrogen or a C₁ to C₆ hydrocarbylgroup.
 9. The product of claim 8 wherein R² is a C₆ to C₃₀ hydrocarbylgroup selected from alkyl, aryl, alkenyl, alkaryl, aralkyl orcycloalkyl.
 10. The product of claim 8 wherein said alkoxylated amine isbis(2-hydroxyethyl)-oleylamine.
 11. The product of claim 1 wherein thediol derived phosphite is prepared from (1) a dihydrocarbyl orfunctionalized phosphite having the general formula: ##STR6## where eachR is the same or different and is a hydrocarbyl group containing from 1to about 20 carbon atoms and (2) a hydrocarbyl or functionalized diolhaving the generalized formula:

    R.sup.1 (OH).sub.2

where R¹ is a hydrocarbyl group containing from 10 to about 30 carbonatoms or a hydrocarbyl group containing from 10 to about 30 carbon atomsand sulfur, nitrogen, oxygen or mixtures thereof.
 12. The product ofclaim 11 wherein R is selected from the group consisting of methyl,ethyl, propyl, butyl, pentyl, hexyl and mixtures thereof.
 13. Theproduct of claim 11 wherein the diol is selected from the groupconsisting of 1,2-decanediol, 1,2-dodecanediol, 1,2-tetradecanediol,1,2-pentadecanediol, 1,2-hexadecanediol, 1,2-heptadecanediol,1,2-octadecanediol or diol esters or mixtures thereof.
 14. The productof claim 13 wherein the diol esters are selected from glycerolmonooleate, trimethylolpropanemonooleate, trimethylolpropanemonostearate, trimethylolpropane monohexanate, glcycerol monohexanoate;pentaerythritol didecanoate and pentaerythritol diisosterate.
 15. Theproduct of claim 11 wherein said phosphite is a cyclic phosphite. 16.The product of claim 1 wherein the hydrocarbyl sulfonate is calciumdinonylnaphthalene sulfonate and the phosphite is a mixedhexadecane-octadecane-1,2-diol phosphite.
 17. The product of claim 1wherein the hydrocarbyl sulfonate is calcium dinonylnaphthalenesulfonate and the phosphite is the reaction product of tributylphosphite and bis(2-hydroxyethyl)oleylamine.
 18. A lubricant compositioncomprising a major proportion of lubricating oil or grease or othersolid lubricant prepared therefrom and a minor multifunctionalantioxidant, friction reducing, anitcorrosion amount of a product ofreaction obtained by reacting a partially acidified hydrocarbylsulfonate having from about 12 to about 32 carbon atoms with adiol-derived phosphite or an amine-derived phosphite having from about10 to about 30 carbon atoms, the reaction being carried out at fromabout 50° C. to about 225° C. using a mole ratio of sulfonate to diol oramine phosphite of from about 10:1 to about 1:10.
 19. The composition ofclaim 18 wherein the hydrocarbyl sulfonate is of the general formula:

    (ArSO.sub.3).sub.n M

wherein n is an integer equal to the valence number of M,M is alkalimetal or alkaline earth metal or a nitrogenous group or mixtures thereofand Ar is a C₁₂ is about a C₃₂ dialkylnaphthalene, dihydrocabylarene oralkylaromatic group.
 20. The composition of claim 19 wherein M is analkaline earth metal.
 21. The composition of claim 20 wherein M iscalcium.
 22. The composition of claim 21 wherein the hydrocarbylsulfonate is calcium dinonylnaphthalene sulfonate.
 23. The compositionof claim 18 wherein the amine phosphite is prepared from amines selectedfrom the group consisting of alkoxylated amines, alkoxylated hydrocarbylamines, alkoxylated hydrocarbyl diamines, or alkoxylated ether aminesand mixtures thereof.
 24. The composition of claim 18 wherein thediol-derived phosphite has the following generalized formula ##STR7##where each R is the same or different and is a hydrocarbyl groupcontaining from 1 to about 20 carbon atoms, and the diol is ahydrocarbyl or functionalized diol having the generalized formula:

    R.sup.1 (OH).sub.2

where R¹ is a hydrocarbyl group containing from 10 to about 30 carbonatoms or a hydrocarbyl group containing from 10 to about 30 carbon atomsand sulfur, nitrogen or oxygen or mixtures thereof.
 25. The compositionof claim 24 wherein R is selected from the group consisting of methyl,ethyl, propyl, butyl, pentyl, hexyl and mixtures thereof.
 26. Thecomposition of claim 24 wherein the diol is selected from the groupsconsisting of 1,2-decanediol, 1,2-dodecanediol, 1,2-tetradecanediol,1,2-pentadecanediol, 1,2-hexadecanediol, 1,2-heptadecanediol,1,2-octadecanediol or diol esters or mixtures thereof.
 27. Thecomposition of claim 26 wherein the diol esters are selected fromglycerol monooleate, trimethylolpropane monostearate, trimethylolpropanemonohexanate, trimethylolpropane monooleate, gylcerol monohexanoate,pentaerythritol didecanoate, and pentaerythritol diisosterate.
 28. Thecomposition of claim 23 made by reacting an alkoxylated amine of theformula: ##STR8## wherein R² is a C₆ to C₃₀ hydrocarbyl group or a C₆ toabout C₃₀ sulfur, nitrogen or oxygen-containing hydrocarbyl group or amixture thereof, R³ is hydrogen or a C₁ to C₆ hydrocarbyl group, and xand y are intergers of from 0 to 50, at least one of which is not 0, anda phosphite is of the formula: ##STR9## wherein R⁴ is a C₁ to C₆hydrocarbyl group and R⁵ is hydrogen or C₁ to C₆ hydrocarbyl.
 29. Thecomposition of claim 28 wherein R² is C₆ to C₃₀ hydrocarbyl and isselected from alkyl, aryl, alkenyl, alkaryl, aralkyl or cycloalkyl. 30.The composition of claim 28 wherein said alkoxylated amine isbis(2-hydroxyethyl)oleylamine.
 31. The composition of claim 18 whereinthe hydrocarbyl sulfonate is calcium dinonylnaphthalene sulfonate andthe amine-phosphite is the reaction product of tributylphosphite andbis(2-hydroxyethyl)oleylamine.
 32. The composition of claim 18 whereinthe hydrocarbyl sulfonate is calcium dinonylnaphthalene sulfonate andthe phosphite is mixed hexadecane-octadecane -1,2-diol phosphite. 33.The composition of claim 18 wherein the lubricant is selected from thegroup consisting of (1) mineral oils (2) synthetic oils or mixture ofsynthetic oils, (3) a mixture of (1) and (2), and (4) a grease preparedfrom any one of (1), (2) or (3).
 34. The composition of claim 33 whereinthe lubricant is a mineral oil.
 35. The composition of claim 33 whereinthe lubricant is a synthetic oil.
 36. The composition of claim 33wherein the lubricant is a mixture of oils defined by (3).
 37. Thecomposition of claim 33 wherein the lubricant is a grease or other solidlubricant prepared from any one of (1), (2) or (3).
 38. A method ofreducing fuel consumption in an internal combustion engine comprisingcontacting and lubricating the moving parts of said engine with acomposition comprising a major proportion of a lubricating oil and afuel reducing/multifunctional additive amount of a product of reactionobtained by reacting a partially acidified hydrocarbyl sulfonate with adiol phosphite or amine-phosphite having from about 10 to about 30carbon atoms, the reaction being carried out at from about 50° C. toabout 225° C. using a mole ratio of sulfonate to diol or amine-phosphiteof from about 10:1 to about 1:10.
 39. A method of providing timedrelease multifunctional friction reducing, antioxidant, antiwear andanticorrosion characteristics to lubricant compositions comprising (1)blending into a major amount of said lubricant composition a minoramount of hydrocarbyl sulfonate and diol-or amine-derived hydrocarbylphosphite, in a mole ratio of sulfonate to phosphite of from about 10:1to 1:10, (2) at least partially acidifying the sulfonate in situ or inservice and thereafter (3) co-reacting the acidified sulfonate and saidphosphite while said lubricant is in use.
 40. The method of claim 39wherein said reaction takes place at temperatures varying from ambientor about 50° C. to about 225° C., at ambient pressures in a lubricantcomposition comprising a major amount of an oil of lubricating viscosityor grease or other solid lubricant prepared therefrom.
 41. The method ofclaim 39 wherein the hydrocarbyl phosphite contains from 10 to about 30carbon atoms and the hydrocarbyl sulfonate contains from 12 to about 32carbon atoms.
 42. The method of claim 39 wherein the hydrocarbylsulfonate is partially acidified as generally described below:

    (ArSO.sub.3).sub.n M+nH.sup.+ →nArSO.sub.3 H+M.sup.n+

where n is an integer equal to the valence number of M,M is alkalimetal, alkaline earth metal or a nitrogenous group or mixture thereofand Ar is a C₁₂ to about a C₃₂ dialkylnaphthalene, dihydrocarbylarene oralkylaromatic group.